Polysulfonate polymers from adamantane bisphenols and disulfonyl chlorides of aromatic substituted ethers

ABSTRACT

NOVEL SLID POLYSULFONATEES HAVING THE STRUCTURE:   -((1,4-PHENYLENE)-(1-R1,5-R2-ADAMANTAN-6,3-YLENE)-(1,4-   PHENYLENE)-O-(1,4-PHENYLENE)-O-SO2-Q-SO2)N-   WHERE R1 AND R2 AR HYDROGEN OR HYDROCARBYL RADICAL HAVING 1 TO 20 CARBON ATOMS, Q REPRESENTS A DIVALENT AROMATIC SUBSTITUTE ETHER RADICAL HAVING 6 TO 20 CARBON ATOMS, AND N REPRESENTS THE NUMBER OF SUCH REPETING UNITS WHICH ARE PRODUCED. THESE THERMOPLASTIC RESINS ARE VALUABLE IN THE MANUFACTURE OF MOLDED AND EXTRUDED ARTICLES.

United States Patent M 3,753,950 POLYSULFONATE POLYMERS FROM ADAMAN-TANE BISPHENOLS AND DISULFONYL CHLO- RIDES OF AROMATKC SUBSTITUTEDETHERS Robert M. Thompson, Wilmington, Del., and Irl N. Duling, WestChester, Pa., assignors to Sun Research and Development (10.,Philadelphia, Pa.

No Drawing. Filed Dec. 30, 1971, Ser. No. 214,408 Int. Cl. C08g 17/08,17/13 US. Cl. 260-49 6 Claims ABSTRACT OF THE DISCLOSURE Novel solidpolysulfonates having the structure:

Patented Aug. 21, 1973 where R and R are hydrogen or hydrocarbyl radicalhaving 1 to 20 carbon atoms, Q represents a divalent aromaticsubstituted ether radical having 6 to 20 carbon atoms, and n representsthe number of such repeating units which are produced. Thesethermoplastic resins are valuable in the manufacture of molded andextruded articles.

BACKGROUND OF THE INVENTION (1) Field of the invention The presentinvention relates to polysulfonates wherein the repeating unit containsan adamantane bisphenol moiety.

(2) Description of the prior art There is a constant eiiort in thepolymer field to provide outstanding new engineering thermoplasticshaving an unusual combination of properties and the ability to retainthese properties under mechanical stress and over a broad temperaturerange. It is also desired that these thermoplastics have excellentresistance to attack by corrosive chemicals. In addition to the aboverequirements, the thermoplastics should exhibit processibility andfrabricability that allow for high-volume manufacturing. It has now beenfound, in accordance with the present invention, novel thermoplasticpolymers which possess the aforementioned properties and in additionhave exceptional oxidation stability and high heat distortiontemperatures.

SUMMARY The present invention is directed to and provides new polymershaving the structuure:

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polysulfonates of theinvention can be prepared from adamantane bisphenols of the structure:

where R and R have the significance previously given and an arylsulfonylhalide. A preferred procedure comprises reacting the adamantanebisphenol and the arylsulfonyl halide in an organic solvent. An aminecatalyst such as triethylene amine is generally employed. The resultingreaction mixture is maintained at a temperature between 35 and 45 C. toproduce a gentle reflux. After the polymerization is complete, thereaction mixture is cooled and poured into 1% hydrochloric acidsolution. The organic layer is separated, extracted with additional acidsolution and washed with water until the water is neutral. The polymeris then precipitated by pouring into an alcohol usually methanol andrecovered by filtering and drying.

Generally, a stoichiometric ratio of adamantane bisphenol to disulfonylchloride of aromatic substituted others is employed although it issometimes desirable to use an excess of the latter. Reaction conditionsof temperature and presure may vary over a wide range. For

1; relative) a7 (inherent) =ln C where 1 (relative): t/t

t =flow time through a viscometer of a liquid reference t=flow timethrough the same viscometer of a dilute solution of a polymer in thereference liquid C=concentration of polymer in solution expressed ingrams/deciliter In the following examples, inherent viscosities wereobtained at a concentration of 0.5 gram per deciliter at 100 F.

The solvent employed was tetrachloroethane. The polymer configurationwas determined by nuclear magnetic resonance and X-ray scan. Thepolysulfonates of the present invention have exceptional oxidationstability and a high heat distortion temperature. The polysulfonates ofthe present invention are thermoplastic and are particularly useful inmolding operations to produce articles such as gears, bearings,instrument and pump housings, impellers and in extrusion operation toproduce articles such as tubes, pipes and rods.

The adamantane bisphenols used as starting materials are described incommonly assigned US. patent application No. 802,661, filed Feb. 26,1969 by Robert E. Moore entitled Adamantane 'Bisphenols and now US. Pat.No. 3,594,427, issued July 29, 1971 and are prepared by reacting acompound of the structure:

where R and R are as previously described and X is independentlyselected from the group consisting of bromo and chloro with an excess ofphenol at a temperature in the range of 125 to 200 C. The reaction timefor preparing the bisphonels will vary, particularly in regard to thetemperature employed, from 4 to 10 hours. In practice, the preferredprocedure is to carry out the reaction at reflux which is around 178-185C. (B.P. phenol 182 C.). At reflux, the reaction requires 5 to 7 hoursfor good yields. No catalyst is required. The reaction takes place in anexcess of phenol which also serves as the solvent for the adamantanereactant and the product. The adamantane bisphenol is most easilyrecovered by cooling the reaction mixture and pouring it into warm water(66-80 C.) thus precipitating the bisphenol and dissolving the phenol.The crystalline material is filtered and recrystallized, for example,from xylene, toluene or isopropanol-water.

The admantane hydrocarbons are well known and their preparation isadequately described in the literature.

The dihalo derivaties can be prepared by reacting the correspondingadmantane hydrocarbon with chlorine or bromine in the presence of AlClor AlBr as disclosed in Stetter and Wulif, German Pat. No. 101,410 andStetter in Angew Chem. International Edit, vol. 1 (1962), No. 6, pp.287-288. The mixed bromo-chloro admantane can be obtained by reacting adibromo adamantane with a chlorine donor such as carbon tetrachloride inthe presence of a Lewis acid catalyst as shown in the copendingapplication of Robert E. Moore, Ser. No. 688,679, filed Dec. 7, 1967,now US. Pat. No. 3,676,017, issued Dec. 7, 1971.

Examples of such suitable reactants to prepare the adamantane bisphenolsare the bridgehead dichloro, dibromo or bromcrchloro derivatives of thefollowing hydrocarbons: adamantane; l-methyladamantane;l-ethyladamantane; 1,3-dimethyladamantane; 1-methyl-3-ethyladamantane;1,3-diethyladamantane; l-n-propyladamantane; l-isopropyladamantane;l-n-butyladamantane; 1,3- di-n-pentyladamantane;l-methyl-3-heptyladamantane; 1- n-decyladamantane; 1-n-decyl-3ethyladamantane; 1- methyl-3-propyladamantane; l-isohexyladamantane; 1-rnethyl-3-cyclohexyladamantane; l-phenyladamantane; 1-methyl-3-phenyladamantane; 1,3-diphenyladamantane; 1- p-tolyladamantane;l-benzyladamantane; and the like.

The disulfonyl halides of aromatic substituted ethers containing from 6to 20 carbon atoms can be prepared by conventional procedures known inthe art. For example, 4,4-bisphenyletherdisulfonyl chloride is preparedby reacting:

Representative of suitable reactants useful in the present invention aredisulfonyl halides of the following aromatic substituted ethers: phenyl,benzyl methyl, benzyl ethyl diphenyl, phenyl methyl, phenyl ethyl,2,8-dibenzofuran, 3,8-dibenzofuran and 6,8-dibenzofuran,3,8-dibenzodioxin and the like.

The polymerization is preferably carried out in a solvent medium. Mostpreferably the solvent should be one in which the reactants are solubleat room temperatures. Suitable solvents for the polymerization includemethylene dichloride, ethanol, benzene, hexane, cyclohexane, carbontetrachloride, tetrachloroethylene, chlorobenzene, o-dichlorobenzene andthe like.

An amine catalyst is preferably employed Suitable catalysts includetrimethylamine, benzyl trimethyl ammonium chloride, tetramethylammoniumchloride and preferably triethylamine.

The following examples are presented to further illustrate theinvention.

EXAMPLE I Into a dried ml. resin kettle, fitted with a stirrer,thermometer, reflux condenser and dropping funnel are charged 7.34 g.(0.02 mole) of 4,4'-diphenyl ether disulfonyl chloride, 6.96 g. (0.02mole) of 1,3-bisphenol- 5,7-dimethyladamantane and 50 ml. of methylenechloride (dried over 5A mole sieve). The reactor is fitted with anitrogen inlet to exclude moisture. Then the stirrer is turned on.Through the dropping funnel, 4.85 g. (0.048 mole) of freshly distilleddry triethylene amine is added slowly over a one-half hour period. Themild exothermic nature of the reaction produced enough heat to maintaina gentle reflux of methylene chloride at this rate of addition. At theend of the addition, external heat is applied by a heating mantle andrefluxing is continued for 1 hour at 39 C. The viscous polymer solutionis cooled and poured into a water solution containing 1% hydrochloricacid and stirred. The organic layer is separated, extracted with aqueousacid solution then equal volumes of water until the water layer isneutral.

that within the scope of the appended claims, the invention may bepracticed by those skilled in the art and having the benefit of thisdisclosure otherwise than is specifically described and exemplifiedherein.

The invention claimed is:

1. A solid moldable and extrudable polymer having the structuralformula:

The polymer is then precipitated by pouring into methanol in a WaringBlender then collected on a Buchner funnel and dried in vacuum at 180 C.The product has an inherent viscosity of (m 1.2 in tetrachloroethane.

Unlike the more usual polysulfonates, this polymer is not brittle buttough. The polymer has a heat distortion temperature of 180 C.

EXAMPLE II Procedure and apparatus are similar to the preceding exampleexcept 69 grams (0.02 mole) 2,8-dibenzofuran disulfonyl chloride arecharged into the reactor in place of the aromatic ether disulfonylchloride of Example 1.

Clear tough films prepared by solution casting or by compression moldingof the polymers have good physical properties.

As mentioned above, these thermoplastic polymers have excellentoxidation stability and a high heat distortion temperature. They may bemolded to produce useful articles like gears, bearings, pulleys,housings, etc. The polymers of this invention may also be extruded byconventional means to produce rods, tubes, pipes, etc.

Pursuant to the requirements of the patent statutes, the principle ofthis invention has been explained and exemplified in a manner so that itcan be readily practiced by those skilled in the art, suchexemplification including what is considered to be the best embodimentof the invention. However, it should be clearly understood,

where R and R are hydrogen or hydrocarbyl radical having 1 to 20 carbonatoms, Q represents a divalent aromatic substituted ether radical having6 to 20 carbon atoms, and n represents the number of repeating units.

2. The polymer according to claim 1 wherein R and R are hydrocarbyl.

3. The polymer according to claim 3 wherein the hydrocarbyl radical has1 to 10 carbon atoms.

4. The polymer according to claim 2 wherein the hydrocarbyl radical isselected from the group consisting of alkyl, cycloalkyl, aryl, alkaryland aralkyl.

5. The polymer according to claim 4 wherein the R and R are selectedfrom the group consisting of methyl and ethyl.

6. The polymer according to claim 5 wherein R and R are methyl.

References Cited UNITED STATES PATENTS 3,658,757 4/1972 Conix et al26049 3,639,351 2/ 1972 Duling et a1 260--75 R WILLIAM H. SHORT, PrimaryExaminer L. L. LEE, Assistant Examiner US. Cl. X.R.

26033.4 R, 33.6 R, 33.8 R

